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The synthesis of poly(ethylene-co-butylene)- block-poly( Me methacrylate) via atom transfer radical polymn. (ATRP) of Me methacrylate onto a poly(ethylene-co-butylene) macroinitiator is described. Copper bromide (CuBr), copper chloride (CuCl) and copper thiocyanate (CuSCN) were applied as active ATRP catalysts with N-pentyl-2-pyridylmethanimine as ligand, in order to study the effect of the copper counter ion on the rate of activation of the bromine-functional polyolefin macroinitiator. The reaction products were subjected to normal phase gradient polymer elution chromatog. (NP-GPEC) in order to sep. residual macroinitiator from the block copolymers. The amt. of residual macroinitiator was monitored for each catalyst system by evaporative light scattering detection, where the chromatograms were normalized on a PS std. which was added to the reaction mixt. before polymn. The rate of activation of the macroinitiator is strongly affected by the copper counter ion and increases in the order CuSCN
Shear et al. (1978) studied this question.